Parvathy M Unnikrishnan, Gopika Premanand, Samar K Das
{"title":"Polyoxometalate-driven assembly of inorganic–organic hybrid materials: Proton conductivity studies","authors":"Parvathy M Unnikrishnan, Gopika Premanand, Samar K Das","doi":"10.1007/s12039-024-02339-6","DOIUrl":null,"url":null,"abstract":"<div><p>A zinc-containing, one-dimensional coordination polymer, [Zn(NH<sub>2</sub>trz)<sub>3</sub>](NO<sub>3</sub>)<sub>2</sub> (1D-CP, NH<sub>2</sub>-trz <span>\\(=\\)</span> 4-amino-4H-1,2,4-triazole) has been employed to synthesize two water-insoluble proton conductors, ZnL-PW<sub>12</sub> and ZnL-SiW<sub>12</sub> (L <span>\\(=\\)</span> 4-amino-4H-1,2,4-triazole), that are formulated as {[Zn(NH<sub>2</sub>trz)<sub>3</sub>](NO<sub>3</sub>)}<sub>2</sub>{HPW<sub>12</sub>O<sub>40</sub>}·4H<sub>2</sub>O and [Zn(NH<sub>2</sub>trz)<sub>3</sub>][NH<sub>3</sub>trz]<sub>2</sub>[SiW<sub>12</sub>O<sub>40</sub>]·10H<sub>2</sub>O, respectively. These proton conductors were prepared through simple room-temperature aqueous reactions involving [Zn(NH<sub>2</sub>trz)<sub>3</sub>](NO<sub>3</sub>)<sub>2</sub> and phosphotungstic or silicotungstic acids, which proceed via aqueous disassembly of the CP, followed by recrystallization into a new phase driven by the addition of heteropolyanions. Here, the Keggin POMs, specifically H<sub>3</sub>PW<sub>12</sub>O<sub>40</sub> and H<sub>4</sub>SiW<sub>12</sub>O<sub>40</sub>, impart enhanced stability to the overall structures of the resulting Zn-complex-POM adducts, ZnL-PW<sub>12</sub> and ZnL-SiW<sub>12</sub>. Upon mixing the aqueous solutions of 1D-CP and POMs, immediate precipitations of the water-insoluble inorganic–organic hybrid products are obtained, the aqueous suspensions of which exhibit acidic pH. This observation prompted us to investigate proton conductivity behaviour of the resulting materials. As anticipated, the isolated products, ZnL-PW<sub>12</sub> and ZnL-SiW<sub>12</sub> exhibit significant proton conductivity values of 5.1 × 10<sup>−3</sup> and 5.6 × 10<sup>−3</sup> S cm<sup>−1</sup>, respectively, at 80°C and 98% relative humidity, demonstrating excellent stability for about 30 h with decent cycling stability over four heating–cooling cycles.</p><h3>Graphical abstract</h3><p>A zinc-based one-dimensional coordination polymer, [Zn(NH<sub>2</sub>-trz)<sub>3</sub>](NO<sub>3</sub>)<sub>2</sub> (1D-CP), was modified into two water-insoluble proton conductors by a process involving the disassembly and subsequent restructuring of the coordination polymer into more stable inorganic–organic hybrids by the addition of phosphotungstic and silicotungstic heteropolyanions. The resulting hybrid materials, ZnL-PW<sub>12</sub> and ZnL-SiW<sub>12</sub> (L = 4-amino-4H-1,2,4-triazole), exhibit significant proton conductivities of 5.1 × 10<sup>−3</sup> and 5.6 × 10<sup>−3</sup> S cm<sup>−1</sup>, respectively, and demonstrate excellent stability for >30 h under the operational conditions.\n</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 1","pages":""},"PeriodicalIF":1.7000,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Sciences","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s12039-024-02339-6","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
A zinc-containing, one-dimensional coordination polymer, [Zn(NH2trz)3](NO3)2 (1D-CP, NH2-trz \(=\) 4-amino-4H-1,2,4-triazole) has been employed to synthesize two water-insoluble proton conductors, ZnL-PW12 and ZnL-SiW12 (L \(=\) 4-amino-4H-1,2,4-triazole), that are formulated as {[Zn(NH2trz)3](NO3)}2{HPW12O40}·4H2O and [Zn(NH2trz)3][NH3trz]2[SiW12O40]·10H2O, respectively. These proton conductors were prepared through simple room-temperature aqueous reactions involving [Zn(NH2trz)3](NO3)2 and phosphotungstic or silicotungstic acids, which proceed via aqueous disassembly of the CP, followed by recrystallization into a new phase driven by the addition of heteropolyanions. Here, the Keggin POMs, specifically H3PW12O40 and H4SiW12O40, impart enhanced stability to the overall structures of the resulting Zn-complex-POM adducts, ZnL-PW12 and ZnL-SiW12. Upon mixing the aqueous solutions of 1D-CP and POMs, immediate precipitations of the water-insoluble inorganic–organic hybrid products are obtained, the aqueous suspensions of which exhibit acidic pH. This observation prompted us to investigate proton conductivity behaviour of the resulting materials. As anticipated, the isolated products, ZnL-PW12 and ZnL-SiW12 exhibit significant proton conductivity values of 5.1 × 10−3 and 5.6 × 10−3 S cm−1, respectively, at 80°C and 98% relative humidity, demonstrating excellent stability for about 30 h with decent cycling stability over four heating–cooling cycles.
Graphical abstract
A zinc-based one-dimensional coordination polymer, [Zn(NH2-trz)3](NO3)2 (1D-CP), was modified into two water-insoluble proton conductors by a process involving the disassembly and subsequent restructuring of the coordination polymer into more stable inorganic–organic hybrids by the addition of phosphotungstic and silicotungstic heteropolyanions. The resulting hybrid materials, ZnL-PW12 and ZnL-SiW12 (L = 4-amino-4H-1,2,4-triazole), exhibit significant proton conductivities of 5.1 × 10−3 and 5.6 × 10−3 S cm−1, respectively, and demonstrate excellent stability for >30 h under the operational conditions.
采用一种含锌的一维配位聚合物[Zn(NH2trz)3](NO3)2 （1D-CP, NH2-trz \(=\) 4-氨基- 4h -1,2,4-三唑）合成了两种不溶于水的质子导体ZnL-PW12和ZnL-SiW12 （L \(=\) 4-氨基- 4h -1,2,4-三唑），分别配制为{[Zn(NH2trz)3](NO3)}2HPW12O40{·4H2O和[Zn(NH2trz)3][NH3trz]2[SiW12O40]·10H2O。这些质子导体是通过[Zn(NH2trz)3](NO3)2和磷钨酸或硅钨酸的简单室温水反应制备的，反应过程是通过CP的水分解，然后在异多阴离子的驱动下再结晶成新相。在这里，Keggin pom，特别是H3PW12O40和H4SiW12O40，增强了所得到的zn -配合物- pom加合物ZnL-PW12和ZnL-SiW12的整体结构稳定性。在将1D-CP和pom的水溶液混合后，获得了水不溶性无机-有机杂化产物的立即沉淀，其水悬浮液具有酸性ph。这一观察结果促使我们研究所得材料的质子电导率行为。正如预期的那样，分离产物ZnL-PW12和ZnL-SiW12在80°C和98°C下分别表现出5.1 × 10−3和5.6 × 10−3 S cm−1的质子电导率值}% relative humidity, demonstrating excellent stability for about 30 h with decent cycling stability over four heating–cooling cycles.Graphical abstractA zinc-based one-dimensional coordination polymer, [Zn(NH2-trz)3](NO3)2 (1D-CP), was modified into two water-insoluble proton conductors by a process involving the disassembly and subsequent restructuring of the coordination polymer into more stable inorganic–organic hybrids by the addition of phosphotungstic and silicotungstic heteropolyanions. The resulting hybrid materials, ZnL-PW12 and ZnL-SiW12 (L = 4-amino-4H-1,2,4-triazole), exhibit significant proton conductivities of 5.1 × 10−3 and 5.6 × 10−3 S cm−1, respectively, and demonstrate excellent stability for >30 h under the operational conditions.
期刊介绍：
Journal of Chemical Sciences is a monthly journal published by the Indian Academy of Sciences. It formed part of the original Proceedings of the Indian Academy of Sciences – Part A, started by the Nobel Laureate Prof C V Raman in 1934, that was split in 1978 into three separate journals. It was renamed as Journal of Chemical Sciences in 2004. The journal publishes original research articles and rapid communications, covering all areas of chemical sciences. A significant feature of the journal is its special issues, brought out from time to time, devoted to conference symposia/proceedings in frontier areas of the subject, held not only in India but also in other countries.
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